Textile sizing solution comprising an interpolymer of a hydrophobic monomer and an unsaturated organic carboxylic monomer and a halogenated hydrocarbon solvent

ABSTRACT

A PROCESS FOR SIZING TEXTILE YARNS WHEREIN THE TEXTILE YARM IS SUBJECTED TO AN ORGANIC SOLVENT SOLUTION OF AN INTERPOLYYMER OF A HYDROPHOBIC MONOMER AND AN UNSATURATED ORGANIC CARBOXYLIC MONOMER CONTAINING 3 TO 9 CARBON ATOMS AND AT LEAST 1 CARBOXYL GROUP, AND THE ORGANIC SOLVENT IS THEREAFTER REMOVED.

United States Patent Ofice 3,728,299 Patented Apr. 17, 1973 3,728,299 TEXTILE SIZING SOLUTION COMPRISING AN INTERPOLYMER OF A HYDROPHOBIC MONO- MER AND AN UNSATURATED ORGANIC CAR- BOXYLIC MONOMER AND A HALOGENATED HYDROCARBON SOLVENT Charles K. Schramm, Westfield, N.J., assignor to Colloids, Inc., Newark, NJ. N Drawing. Filed Jan. 22, 1971, Ser. No. 108,956 Int. Cl. C08f 45/30; D06m 15/00 US. Cl. 260-33.8 UA 8 Claims ABSTRACT OF THE DISCLOSURE A process for sizing textile yarns wherein the textile yarn is subjected to an organic solvent solution of an interpolymer of a hydrophobic monomer and an unsaturated organic carboxylic monomer containing 3 to 9 carbon atoms and at least 1 carboxyl group, and the organic solvent is thereafter removed.

BACKGROUND OF THE INVENTION The treating of textile yarns with an aqueous sizing solution such as a crotonic acid-vinyl acetate copolymer, gelatin, or rosin to protect the textile yarn during weaving or knitting and to prevent sticking to the mechanical moving parts of a loom or knitting machine is well known. For example, US. Pat. 2,806,020 teaches that a low molecular weight copolymer of vinyl acetate and 2 to 10 mole percent crotonic acid can be dissolved in aqueous solutions of caustic soda or sodium carbonate and employed as a textile sizing. However, the application of a sizing material from an aqueous solution raises problems which have been magnified with the advent of new weaving and knitting techniques. The recently introduced water-jet loom employs streams or jets ofwater droplets to transport the strands of yarn during weaving which results in a moisture saturated atmosphere surrounding the loom. As a result, a size which has been applied from an aqueous solution tends to swell or redissolve with a resulting loss of abrasion resistance of the sized yarn. Additionally, the use of aqueous sizing solutions results in a liquid waste disposal problem both in sizing as well as desizing and finishing of the resulting cloth.

Accordingly, it is the object of this invention to provide a composition and a process for sizing textiles employing an organic solution which will substantially improve size performance qualities in conventional mechanical looms, as well as enhance size performance when a water-jet loom is employed. These and other objects will become apparent to those skilled in the art from the following de tailed description.

SUMMARY OF THE INVENTION This invention relates to a process of sizing textiles and to an organic solvent sizing solution employed therein. More particularly, the invention relates to a process for sizing of textile yarns by subjecting the yarn to an organic solvent solution of an interpolymer of a hydrophobic compound and an unsaturated organic carboxylic compound containing at least one carboxyl group and thereafter removing the solvent to provide the sized material, and to the organic solvent size solution employed therein.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with the invention, there is provided an organic solvent solution of an interpolymer of a hydrophobic monomer and an unsaturated organic carboxylic monomer. Any organic solvent for the interpolymer can be employed, such as, e.g., any of the conventional drycleaning solvents. It is preferred to use the relatively nontoxic, non-flashing chlorinated hydrocarbons such as trichloroethane, trichloroethylene, perchloroethylene, methylene chloride, and the like. The most preferred organic solvents are trichloroethane and trichloroethylene.

The interpolymers of the invention can be prepared from a hydrophobic compound such as vinyl acetate, vinyl chloride, styrene, acrylate esters and methacrylate esters, a larger variety of unsaturated carboxylic compounds, and mixtures thereof. The preferred interpolymers are copolymers of the hydophobic compound and carboxylic compound. Among the acrylate esters that can be used are methyl acrylate, ethyl acrylate, butyl acrylate, n-hexyl acrylate, 1,1-dihydroperfluorobutyl acrylate, beuzyl acrylate, cyclohexyl acrylate, phenylethyl acrylate, and the like. Among the methacrylate esters which can be used are methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, allyl methacrylate, ethylene methacrylate, n-amyl methacrylate, ethylene diglycoldiacrylate, and the like. In general, the ester moiety of the acrylate and methacrylate esters are alkyl, cycloalkyl, alkylene, aryl, and aralkyl radicals of 1 to 15 carbon atoms.

The unsaturated carboxylic compounds which are copolymerized with the hydrophobic compound usually contain about 3 to 9 carbon atoms and have at least 1 carboxyl group. The compound can be an ethylenically unsaturated monocarboxylic acid, polycarboxylic acid, partial ester of a polycarboxylic acid, and the like. Typical acids include acrylic acid; butenic acids such as crotonic acid, isocrotonic acid, methacrylic acid and vinyl acetic acid; pentenic acids such as tiglic acid and angelic acid;

' fumaric acid, maleic acid; itaconic acid; and the like. Of

the foregoing acids, crotonic acid is preferred.

The partial esters of the unsaturated polycarboxylic acids are preferably the alkyl half esters in which the alkyl group contains 1 to 4 carbon atoms. Typicalcompounds include methyl acid maleate; ethyl acid maleate; propyl acid maleate; butyl acid maleate, isobutyl acid maleate; methyl acid fumarate; secondary butyl acid fumarate; methyl acid citraconate; butyl acid citraconate; ethyl acid chlormaleate; butyl acid chlormaleate; methyl acid itaconate; butyl acid itaconate; and the: like. Of the foregoing partial esters, the maleic acid half esters are preferred.

The carboxylic compound and hydrophobic compound can be interpolymerized by any of the processes known in the art such as, for example, taught in the aforementioned US. Patent 2,806,020. The carboxylic compound is used in an amount sufficient to provide up to about 10 Weight percent of the compound in the copolymer. The carboxylic content of the polymer is subject to competing demands. The adhesion of the polymer to the textile yarns is increased as the carboxylation is increased and the solubility in the organic solvent is increased as the carboxylation is decreased. Therefore, it is preferred to employ a copolymer containing about 0.1 to 7 weight percent carboxylic compound and most preferably, containing about 0.5 to 4 weight percent carboxylic compound based on the total weight of the copolymer. In general, the interpolymers of the present invention have a molecular weight between 1000 and 1,000,000 and preferably between 10,000 and 250,000. The viscosity in 2B ethanol of a molar solution is about 1 to 1000 cps., and preferably about to 100 cps.

While it is possible to employ an organic solution having an interpolymer content of a fraction of a percent to a saturated solution, the interpolymer concentration is generally maintained at about 1 to 25 weight percent based on the total weight of the solution. When filament yarn is to be sized, the interpolymer concentration is preferably about 3 to weight percent and when spun yarn is to be sized, the interpolymer concentration is preferably about 5 to 25 weight percent. It is important that the copolymers be completely soluble in the solvent because gels (incompletely dissolved particles) will cause broken yarn filaments during weaving or knitting. Without being limited to theory, it is believed that the interpolymers are soluble in the organic solvent as the result of a balancing of the slight polarity of the interpolymer introduced by carboxyl group with the slight polarity of the organic solvent.

The organic solvent size solutions of the invention are employed in sizing textile yarns and are especially suitable for sizing textile warp yarns. The applied size has good adhesion and provides excellent abrasion protection to textile yarns such as cotton; wool; worsted; polyamides such as nylon; viscose; rayon; polyesters; acrylics; acetates; triacetates such as Arnel; polyolefins, e.g., polypropylene or polyethylene; fiberglass (glass fiber); and blends of these natural and synthetic fibers such as cotton/polyester or wool/polyester. The superior properties of, for example, a vinyl acetate-crotonic acid copolymer of theinvention applied from an organic solvent system, with all textile yarns is particularly surprising since the conventional vinyl acetate-crotonic acid copolymers applied from an aqueous system are inferior to polyacrylic acid as a size for such yarns as nylon and acrylics.

The amount of sizing composition picked up by the yarns is generally close to 100% when the size is applied from the organic solvent solution. This is 2-3 times of the amount of pick-up generally obtained when the size is applied from an aqueous system of the same polymer concentration. More importantly, on hydrophobic yarns such as nylon, polyester and polyolefins, application of the size from an organic system rather than an aqueous system enhances size penetration into the fiber bundle and gives more ideal size placement for better protection against abrasion during weaving.

The sizing composition can be applied to textile yarns by a variety of procedures and using different kinds of equipment. While the individual steps and equipment can vary with the different procedures, in each case, the textile is immersed in the organic solvent size solution and the solvent is thereafter removed by evaporation or vaporization to provide the sized material. In one suitable procedure, a multitude of textile yarn ends from a creel are 7 passed through a size box containing the organic solvent size solution. Thereafter, the yarn ends are passed between squeeze rolls to remove excess solution and then passed over a multitude of drying cans which are usually maintained at a temperature of about 150-230 F. Also, textile yarns in the form of skeins can be sized by dipping the skeins in the size composition, removing the skeins and then drying the skeins.

One important advantage of the present invention is that the size can be easily removed from the woven or knitted fabric. The fabric can be immersed in the organic solvent and the interpolymer size will dissolve therein. The resulting solution can be re-used in sizing yarns or the components thereof can be recovered by conventional separation techniques. Additionally, if desired, the inter- 4 polymer size can be scoured from the woven or knitted fabric with warm or hot mildly alkaline aqueous solutions.

The following examples serve to further illustrate the invention but are not intended to limit it. Unless otherwise specified throughout this specification and claims, all temperatures are in degrees centigrade and all parts are expressed in parts by Weight. The properties of the sized yarn were determined by abrading the yarn by rubbing. The ability of the sized yarn to form a loop Without filament separation and the appearance of the sized yarn edges at the breaking point was observed. The number of rubs necessary to remove the size and to fray the yarn was recorded. Also, the number of rubs needed to abrade (fray) and to break yarn which had been wet with water was also recorded. The stiffness of the sized yarn was rated on a scale from 1 (very limp) to 5 (very stifi).

Example 1 10% solutions of two resins in trichloroethane were prepared. The yarns listed below were immersed in the solutions at room temperature, removed from the solutions, and the trichloroethane was allowed to evaporate. The properties of the sized yarns are listed in Table I.

TABLE I Nylon Polyester Acetate A. Copolymer of vinyl acetate and 3% crotonic acid having a molar viscosity in 2B ethanol of 15 cps.

Loop Excellent- Excellent- Excellent. Appearance of yarn edge at break Fair-poor- 0....... Do. Abrasion, number of rubs to fray-.- 50 100+. Wet abrasion, number of rubs to fray 100+ 100+ 80. Wet break, number of rubs to break. 100+ 100+ 80. Stifiness 1. 2+ 1.

Yarn

B. Copolymer of vinyl acetate and 3% crotonic acid having a molar viscosity in 2B ethanol of 25 cps.

Loop Excellent- Excellent- Excellent. Appearance of yarn edge at break.-. Fair do Do. Abrasion, number of rubs to fray-.- 30 100+ 100+. Wet abrasion, number of rubs to ay 100+ 100+ 100+. Wet break, number of rubs to break- 100+ 100+ 100+. Stiffness 1 1 1.

Example 1 was repeated except that trichloroethylene was employed as the solvent in place of the trichloroethane. The properties observed are reported in Table II.

TABLE II Nylon Polyester Acetate A. Copolymer of vinyl acetate and 3% erotonic acid having a molar Yarn viscosity in 2B ethanol of 15 cps.

Loop Excellent- Excellent- Excellent. Appearance of yarn edge at; break Good-fair- .do Abrasion, number of rubs to fray-.- 45 100+ Wet abrasion, number of rubs to ay 100+ Wet break, number of rubs to break. 100+ Sh'finess 1 B. Copolymer of vinyl acetate and 3% crotonic acid having a molar viscosity in 2B ethanol of 25 cps.

Loop Excellent. Excellent- Excellent. Appearance of yarn edge at break..- Good do Do. Abrasion, number of rubs to fray 50 60 100+. Wet abrasion, number of rubs to fray 100+ Wet break, number of rubs to break 100+ Stiffness 1 When 10% solutions of polyvinyl acetate having a molar viscosity of 20 cps. in 2B ethanol, and of a copolymer of vinyl acetate and 25% isobutyl maleate in the trichloroethylene solvent were prepared, the presence of gels were observed. These incompletely dissolved polymer particles will cause broken yarn filaments during weaving or knitting.

Examples 3-8 Following the procedure of Example 1, rayon acrylics, cotton and wool can be sized by employing 10% solutions in perchloroethylene or methylene chloride of the following copolymers:

vinyl acetate and 3.7% crotonic acid (acid number of vinyl acetate and 5% crotonic acid (acid number of 33);

vinyl acetate and 2% monomethyl maleate (acid number vinyl acetate and 0.5% monomethyl maleate (acid number of 2);

vinyl acetate and 3.3% monoisobutyl maleate (acid number of 10); and

vinyl acetate and 1% monoisobutyl maleate (acid number of 3.3).

Examples 9-11 Following the procedure of Example 1, cotton can be sized employing a solution of the following interpolymers in either trichloroethane or trichloroethylene:

copolymer of styrene and 5% monomethyl maleate;

copolymer of styrene and 3% acrylic acid; and

terpolymer of 86% vinyl acetate, 10% ethyl acrylate and 4% monomethyl maleate.

Various changes and modifications can be made in the composition and process of the invention without departing from the spirit and scope thereof. The various embodiments disclosed herein serve to further illustrate the invention but are not intended to limit it.

-I claim:

1. A composition comprising an organic solvent solution of about 1 to 25 weight percent based on the total weight of the solution of an interpolymer of a hydrophobic monomer selected from the group consisting of vinyl acetate, acrylate esters and methacrylate esters wherein said ester moiety is alkyl, cycloalkyl, alkylene, aryl and aralkyl radicals of 1 to 15 carbon atoms, and up to about 10 weight percent of an unsaturated organic carboxylic compound having at least one carboxyl group and about 3 to 9 carbon atoms, said interpolymer having a molecular weight between 1000 and 1,000,000, and wherein said organic solvent is selected from the group consisting of trichloroethane, trichloroethylene, perchloroethylene and methylene chloride.

2. The composition of claim 1 wherein the interpolymer is a copolymer, wherein the hydrophobic monomer is vinyl acetate, and wherein the carboxylic compound is crotonic acid.

3. The composition of claim 2 wherein the crotonic acid content of the copolymer is about 0.1 to 7 weight percent based on the weight of the copolymer and the copolymer is about 2 to 25 weight percent of the solution based on the total weight of the solution.

4. The composition of claim 3 wherein the crotonic acid is about 0.5 to 4 weight percent of the copolymer and the copolymer has a molecular weight between 10,000 and 250,000.

5. The composition of claim 4 wherein the solvent is trichloroethane.

6. The composition of claim 4 wherein the solvent is trichloroethylene.

7. The composition of claim 1 wherein the interpolymer is about 3 to 10 Weight percent of the solution based on the total weight of the solution, the unsaturated organic carboxylic compound is about 0.1 to 7 weight percent of the interpolymer and the interpolymer has a molecular weight between 10,000 and 250,000.

8. The composition of claim 1 wherein the interpolymer is about 5 to 25 weight percent of the solution based on the total weight of the solution, the unsaturated organic carboxylic compound is about 0.1 to 7 Weight percent of the interpolymer and the interpolymer has a molecular weight between 10,000 and 250,000.

References Cited UNITED STATES PATENTS 2,263,598 11/1941 Starck et al. 260-85.7 2,806,020 9/ 1957 Scott et a1. 260--85.7 3,247,144 4/ 1966 Masters et a1. 260-] 3,497,480 2/1970 Bauer et a1. 26033.8-UA

ALLAN LIEBERMAN, Primary Examiner US. Cl. X.R. 117-1395 

